JP5145682B2 - Permeated water nozzle for reverse osmosis membrane module and reverse osmosis membrane module - Google Patents
Permeated water nozzle for reverse osmosis membrane module and reverse osmosis membrane module Download PDFInfo
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- JP5145682B2 JP5145682B2 JP2006270480A JP2006270480A JP5145682B2 JP 5145682 B2 JP5145682 B2 JP 5145682B2 JP 2006270480 A JP2006270480 A JP 2006270480A JP 2006270480 A JP2006270480 A JP 2006270480A JP 5145682 B2 JP5145682 B2 JP 5145682B2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 97
- 239000012528 membrane Substances 0.000 title claims description 88
- 238000001223 reverse osmosis Methods 0.000 title claims description 63
- 229920005989 resin Polymers 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 25
- 239000012510 hollow fiber Substances 0.000 claims description 24
- 239000013535 sea water Substances 0.000 claims description 14
- 238000010612 desalination reaction Methods 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 239000012466 permeate Substances 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 5
- 229920002301 cellulose acetate Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 5
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 229930182556 Polyacetal Natural products 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- -1 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000002184 metal Substances 0.000 description 9
- 239000008400 supply water Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/138—Water desalination using renewable energy
- Y02A20/144—Wave energy
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Description
本発明は、脱塩等に用いられる逆浸透膜モジュールに関する発明である。特に本発明は、海水を淡水化する場合や酸性水溶液を処理する場合等、逆浸透膜の透過水の腐食性が高い状態であっても、透過水ノズルが腐食しにくく耐久性に優れる逆浸透膜モジュールを提供することを目的とする。 The present invention relates to a reverse osmosis membrane module used for desalting and the like. In particular, the present invention is a reverse osmosis in which the permeated water nozzle is hardly corroded and has excellent durability even when the permeated water of the reverse osmosis membrane is highly corrosive, such as when desalinating seawater or treating an acidic aqueous solution. An object is to provide a membrane module.
逆浸透法は、海水及びかん水の淡水化、半導体工業及び医薬品工業用の純水、超純水の製造、都市排水処理等の幅広い分野で利用されている。蒸発法、電気透析法と比較して省エネルギーの点で有利であり、広く普及が進んでいる。特に、中空糸型逆浸透膜は、単位容積当たりの膜面積を大きくできるため、膜分離操作に適した形状であり、例えば、逆浸透膜による海水淡水化分野では広く用いられている。以下、主に海水淡水化分野で使用される状況を例にとり、説明を行う。 The reverse osmosis method is used in a wide range of fields such as desalination of seawater and brine, production of pure water for the semiconductor industry and pharmaceutical industry, ultrapure water, and municipal wastewater treatment. Compared to the evaporation method and electrodialysis method, it is advantageous in terms of energy saving and is widely spread. In particular, since the hollow fiber type reverse osmosis membrane can increase the membrane area per unit volume, the hollow fiber type reverse osmosis membrane has a shape suitable for membrane separation operation, and is widely used, for example, in the field of seawater desalination using a reverse osmosis membrane. In the following, description will be given mainly taking the situation of use in the seawater desalination field as an example.
逆浸透法で処理される場合は逆浸透膜モジュールが用いられる。一般には、供給水ノズルから供給された供給水は逆浸透膜モジュールへ供給され、逆浸透膜を透過した水は透過水ノズルから取りだされ、透過せずに濃縮された水は濃縮水ノズルから取り出される。 In the case of processing by the reverse osmosis method, a reverse osmosis membrane module is used. In general, the supply water supplied from the supply water nozzle is supplied to the reverse osmosis membrane module, the water that has permeated the reverse osmosis membrane is taken out from the permeate nozzle, and the water that has not been permeated is concentrated from the concentrate water nozzle. It is taken out.
従来、供給水ノズル、濃縮水ノズルは高塩濃度水と接触するために腐食により損傷しやすく、耐腐食性ステンレス等の材料が用いられている。一方、透過水ノズルが接触するのは逆浸透膜の透過水であり、これは、供給水や濃縮水に比べて塩濃度が低いため、腐食による損傷は発生しにくいと考えられていた。 Conventionally, since the supply water nozzle and the concentrated water nozzle are in contact with high salt concentration water, they are easily damaged by corrosion, and materials such as corrosion resistant stainless steel have been used. On the other hand, the permeated water nozzle is in contact with the permeated water of the reverse osmosis membrane, which has a lower salt concentration than that of the feed water and concentrated water, and is thought to be less likely to be damaged by corrosion.
しかしながら、海水淡水化に用いる場合などは、透過水の塩濃度は５００ｍｇ／Ｌ程度となることは一般的であり、多くの逆浸透膜モジュールが設置されている大型海水淡水化施設では、運転が長期に及ぶとともに膜モジュールの除去性能にばらつきが生じ、除去性能の低い膜モジュールの透過水では１０００ｍｇ／Ｌ以上の高塩濃度となる場合もある。特に、個々の膜エレメントの透過水を個別に取り出すことのできる逆浸透膜モジュール構造の場合には、他の膜エレメントの低塩濃度の透過水で希釈されることなくこの高塩濃度の透過水が透過水ノズルに直接接触する。透過水ノズルに金属製の部材を用いた場合、高塩濃度の透過水と長期間接触することにより、腐食による損傷が発生する場合があり、特に、透過水ノズルと配管との接続部に発生する隙間腐食が発生する場合が多い。耐腐食性のステンレス等を用いることでこれらを防止することは可能であるが、費用が高くなり問題である。 However, when used for seawater desalination, the salt concentration of the permeated water is generally about 500 mg / L. In large-scale seawater desalination facilities where many reverse osmosis membrane modules are installed, operation is not possible. The removal performance of the membrane module varies over a long period of time, and the permeated water of the membrane module having a low removal performance may have a high salt concentration of 1000 mg / L or more. In particular, in the case of a reverse osmosis membrane module structure in which the permeated water of each membrane element can be individually taken out, this high salt concentration permeated water is not diluted with the low salt concentration permeated water of other membrane elements. Directly contacts the permeate nozzle. When a metal member is used for the permeate nozzle, damage due to corrosion may occur due to long-term contact with permeate having a high salt concentration, especially at the connection between the permeate nozzle and the pipe. In many cases, crevice corrosion occurs. Although it is possible to prevent these by using a corrosion-resistant stainless steel or the like, the cost becomes high and this is a problem.
また、腐食発生防止のために硬質塩化ビニル等の樹脂製の透過水ノズルを用いることが開示されているが、金属配管との接続部で、強度が不十分なため変形・破損し、水もれの原因となる場合がある。 In addition, it is disclosed that a permeated water nozzle made of resin such as hard vinyl chloride is used to prevent the occurrence of corrosion. It may cause this.
本発明は、このような点に鑑みてなされたもので、塩水との接触による腐食の損傷が発生せず、かつ金属配管との接続に際し、損傷を受けることの無い透過水ノズルを有する逆浸透膜モジュールを提供することを目的とする。 The present invention has been made in view of such points, and reverse osmosis has a permeated water nozzle that does not cause corrosion damage due to contact with salt water and that is not damaged when connected to metal piping. An object is to provide a membrane module.
本発明者らは、上記課題を克服すべく鋭意検討を重ねた結果、本発明に到達した。すなわち、本願発明は下記の構成を有するものである。
（１）シャルピー衝撃強さが４kJ／m2以上かつ弾性率４GPa以上かつ吸水率０．５％以下の樹脂系の材料からなり、前記樹脂系の材料がポリフェニレンサルファイド樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルイミド樹脂、ポリブチレンテレフタレート樹脂、ポリアセタール樹脂の群から選ばれる少なくとも１種をガラス繊維強化したものであることを特徴とする逆浸透膜モジュール用透過水ノズル。
（２）該逆浸透膜モジュールが海水淡水化用の逆浸透膜モジュールであることを特徴とする（１）に記載の逆浸透膜モジュール用透過水ノズル。
（３）該逆浸透膜モジュールが２本以下の逆浸透膜エレメントを圧力容器に装填したものであり、各逆浸透膜エレメントの透過水が個別の透過水ノズルにより取り出されることを特徴とする（１）または（２）に記載の逆浸透膜モジュール用透過水ノズル。
（４）（１）から（３）いずれかに記載の透過水ノズルが装着されていることを特徴とする逆浸透膜モジュール。
（５）該逆浸透膜が酢酸セルロース系高分子からなる中空糸型逆浸透膜からなることを特徴とする（４）に記載の逆浸透膜モジュール。
The inventors of the present invention have arrived at the present invention as a result of intensive studies to overcome the above problems. That is, the present invention has the following configuration.
(1) Charpy impact strength Ri Do from 4 kJ / m 2 or more and an elastic modulus 4GPa or more and the material of the water absorption of 0.5% or less of the resin, the resin-based material is polyphenylene sulfide resin, polyether ether ketone resin , polyetherimide resin, polybutylene terephthalate resin, a reverse osmosis membrane permeated water nozzle module, characterized in der Rukoto those reinforced glass fiber at least one selected from the group consisting of polyacetal resin.
(2) The permeated water nozzle for a reverse osmosis membrane module according to (1), wherein the reverse osmosis membrane module is a reverse osmosis membrane module for seawater desalination.
(3) The reverse osmosis membrane module is obtained by loading two or less reverse osmosis membrane elements into a pressure vessel, and the permeated water of each reverse osmosis membrane element is taken out by an individual permeated water nozzle ( A permeated water nozzle for a reverse osmosis membrane module according to 1) or (2) .
(4) A reverse osmosis membrane module comprising the permeated water nozzle according to any one of (1) to ( 3) .
(5) The reverse osmosis membrane module according to ( 4) , wherein the reverse osmosis membrane is a hollow fiber type reverse osmosis membrane made of a cellulose acetate polymer.
逆浸透膜モジュールにシャルピー衝撃強さ（ノッチ付き）が４kＪ／m2以上かつ曲げ弾性率４GPa以上かつ吸水率０．５％以下の樹脂系の材料からなる透過水ノズルを用いることにより、塩水による腐食による損傷を防止でき、かつ、金属配管との接続に際しての機械的損傷も抑制可能で、水漏れが防止可能である。特に、海水淡水化に用いる逆浸透膜モジュールに適するほか、酸性水溶液等の腐食性の強い透過水が得られる逆浸透プロセスで用いられる逆浸透膜モジュールへの適用が好適である。 By using a permeated water nozzle made of a resin material with a Charpy impact strength (notched) of 4 kJ / m 2 or more, a flexural modulus of 4 GPa or more and a water absorption of 0.5% or less for the reverse osmosis membrane module, Damage due to corrosion can be prevented, and mechanical damage at the time of connection with metal piping can be suppressed, and water leakage can be prevented. In particular, it is suitable for a reverse osmosis membrane module used for a reverse osmosis membrane module used for seawater desalination, and also for a reverse osmosis membrane module used in a reverse osmosis process for obtaining a corrosive permeated water such as an acidic aqueous solution.
本発明における逆浸透膜とは、数十ダルトンの分子量の分離特性を有する領域の分離膜であり、具体的には、０．５ＭＰａ以上の操作圧力で、食塩を９０％以上、除去可能であるものである。海水淡水化に使用される逆浸透膜は、操作圧力が大きく、また、食塩の除去率は９９％以上が一般的である。 The reverse osmosis membrane in the present invention is a separation membrane in a region having a molecular weight separation characteristic of several tens of daltons, and specifically, 90% or more of salt can be removed at an operating pressure of 0.5 MPa or more. Is. The reverse osmosis membrane used for seawater desalination has a large operating pressure, and the removal rate of salt is generally 99% or more.
本発明におけるシャルピー衝撃強さは、透過水ノズルの成型に用いる樹脂系の材料を、ＩＳＯ１７９：１９３３に記載されているＩＳＯ１７９／１ｅＡにより２３℃で測定した値とする。シャルピー衝撃強さは耐衝撃性の指標であり、この値が大きいほど耐衝撃性が大きく、衝撃による損傷を受けにくい。透過水ノズルは、金属配管と接続して用いられ、逆浸透膜装置の運転の起動・停止時に生じる振動や、透過水ノズルの装着・脱着の際の接触の繰り返し等により、機械的な衝撃にさらされるので、耐衝撃性が高いことが必要となる。また、透過水ノズルはその機能上、Oリング溝やビクトリックジョイント用溝等の溝加工を施されることが多く、このため、ノッチ付き試料で測定された衝撃強さが高いことが要求される。本発明で用いられる樹脂系の材料のシャルピー衝撃強さは、好ましくは４ｋＪ／ｍ2以上であり、より好ましくは７ｋＪ／ｍ2以上である。この値が小さいと、透過水ノズルが亀裂や断裂等の損傷を受け易くなるので好ましくない。本発明における樹脂系材料のシャルピー衝撃強さは高いほど好ましい。このため、シャルピー衝撃強さには特に上限を定めないが、一般的にシャルピー衝撃強さの高い材料は、後述する弾性率が低くなる場合が多いので、いたずらにシャルピー衝撃強さの高さを求めるよりも、両者の要求性能を満たすことが重要である。 The Charpy impact strength in the present invention is a value obtained by measuring a resin material used for molding a permeated water nozzle at 23 ° C. according to ISO 179 / 1eA described in ISO 179: 1933. Charpy impact strength is an index of impact resistance. The larger the value, the greater the impact resistance and the less likely it is damaged by impact. Permeated water nozzles are used in connection with metal pipes, and are subject to mechanical shock due to vibrations that occur when starting and stopping the operation of the reverse osmosis membrane device and repeated contact when the permeated water nozzle is installed and removed. Because it is exposed, it must have high impact resistance. In addition, the permeated water nozzles are often subjected to groove processing such as O-ring grooves and Victoria joint grooves due to their functions, which requires a high impact strength measured with a notched sample. The The Charpy impact strength of the resin material used in the present invention is preferably 4 kJ / m 2 or more, more preferably 7 kJ / m 2 or more. If this value is small, the permeated water nozzle is susceptible to damage such as cracks and tears, which is not preferable. The higher the Charpy impact strength of the resin material in the present invention, the better. For this reason, there is no particular upper limit for Charpy impact strength, but in general materials with high Charpy impact strength often have a lower elastic modulus, which will be described later. It is more important to satisfy the required performance than both.
本発明における弾性率は、透過水ノズルの成型に用いる樹脂系の材料の試験片の曲げ弾性率をＩＳＯ１７８：１９９３に記載の方法により２３℃で測定した値とする。透過水ノズルは、その使用中に、透過水の圧力による内圧を受けるほか、配管との接続に起因する外力を受ける。弾性率はこれらの応力に対抗して変形せず形態を維持する能力の指標であり、この値が高いほど変形しにくい。弾性率は、その測定方法により、引張弾性率、曲げ弾性率、圧縮弾性率等があるが、本発明ではこれらを代表して曲げ弾性率を指標として用いることとする。本発明における樹脂系の材料の曲げ弾性率は４GPa以上が好ましく、7GPａ以上であればさらに好ましい。弾性率が低いと、透過水ノズルの装脱着の際に受ける外力や使用中に受ける内圧等によって、変形しあるいは亀裂を生じ、これにより水漏れを生じる恐れがある。本発明における樹脂系の材料の曲げ弾性率は高いほど好ましい。このため曲げ弾性率には特に上限を定めないが、一般的に高弾性率の材料は耐衝撃性が低い場合が多いので、既述のとおり、いたずらに高弾性率であるよりも、両者の要求性能を満たすことが重要である。 The elastic modulus in the present invention is a value obtained by measuring the bending elastic modulus of a test piece of a resin material used for molding a permeated water nozzle at 23 ° C. according to the method described in ISO 178: 1993. During its use, the permeated water nozzle receives an internal pressure due to the pressure of the permeated water and also receives an external force resulting from the connection with the piping. The elastic modulus is an index of the ability to maintain the shape without being deformed against these stresses, and the higher this value, the harder it is to deform. The elastic modulus includes a tensile elastic modulus, a bending elastic modulus, a compressive elastic modulus, and the like depending on the measurement method. In the present invention, the bending elastic modulus is used as an index on behalf of these. The flexural modulus of the resin material in the present invention is preferably 4 GPa or more, and more preferably 7 GPa or more. When the elastic modulus is low, there is a risk of deformation or cracking due to an external force received when the permeated water nozzle is attached or detached, an internal pressure received during use, etc., thereby causing water leakage. The higher the flexural modulus of the resin material in the present invention, the better. For this reason, no particular upper limit is set for the flexural modulus, but in general, a material with a high elastic modulus often has a low impact resistance. It is important to meet the required performance.
本発明における吸水率は、透過水ノズルの成型に用いる樹脂系の材料の試験片を、ＩＳＯ６２：１９９９に記載のA法により２３℃で２４時間浸漬して測定された値とする。透過水ノズルは使用中、常時水と接触して使用されるため、水との接触によって寸法や物性が大きく変化するものは使用に耐えない。本発明においては、水との接触に対する安定性の指標として、吸水率を使用する。吸水率の高い材料は、吸水による寸法変化や物性変化が大きく、本発明の樹脂系の材料としては適さないからである。本発明における樹脂系の材料の吸水率は０．５％以下が好ましく、０．３％以下がさらに好ましい。０．０３％以下であればさらに好ましい。 The water absorption rate in the present invention is a value measured by immersing a test piece of a resin material used for molding a permeated water nozzle at 23 ° C. for 24 hours by the method A described in ISO 62: 1999. Since the permeated water nozzle is always used in contact with water during use, a nozzle whose dimensions and physical properties greatly change due to contact with water cannot be used. In the present invention, water absorption is used as an indicator of stability against contact with water. This is because a material having a high water absorption rate has a large dimensional change and physical property change due to water absorption, and is not suitable as the resin material of the present invention. The water absorption rate of the resin material in the present invention is preferably 0.5% or less, more preferably 0.3% or less. More preferably, it is 0.03% or less.
本発明における樹脂系の材料とは、樹脂を含む材料であれば特に限定されない。２種類以上の異種の樹脂の混合物やポリマーアロイであってもよく、充填材を包含した複合材料であってもよい。充填材の材質は、無機物、有機物あるいはそれらの混合物等、種々のものがあるが、いずれのものであっても良い。また、充填材には繊維状、粒状、板状等の種々の形状があるが、いずれの形状であってもよい。充填材の配合量には特に制限はないが、１０〜５０％とすることが好適である。シャルピー衝撃強さ、曲げ弾性率、吸水率のいずれについても本発明の要求特性を満たす樹脂系の材料の好適な例として、充填材としてガラス繊維や炭素繊維等の強化繊維を含むエンジニアリングプラスチックが挙げられる。ポリフェニレンサルファイド樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルイミド樹脂、ポリブチレンテレフタレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリアセタール樹脂やそれらの変性樹脂等をガラス繊維強化した樹脂は、本発明において好適な樹脂系の材料である。特に、ガラス繊維強化ポリフェニレンサルファイド樹脂は、シャルピー衝撃強さおよび曲げ弾性率が高くかつ吸水率が低いのみならず、引っ張りクリープ寿命が長く、繰り返し振動疲労が小さい特性があり、透過水ノズルの材料として特に好ましい。 The resin material in the present invention is not particularly limited as long as it is a material containing a resin. It may be a mixture of two or more different kinds of resins, a polymer alloy, or a composite material including a filler. There are various kinds of filler materials such as inorganic substances, organic substances or mixtures thereof, and any of these may be used. In addition, the filler has various shapes such as a fiber shape, a granular shape, and a plate shape, and may be any shape. Although there is no restriction | limiting in particular in the compounding quantity of a filler, It is suitable to set it as 10 to 50%. As a suitable example of a resin-based material that satisfies the required characteristics of the present invention for any of Charpy impact strength, flexural modulus, and water absorption, engineering plastics that contain reinforcing fibers such as glass fibers and carbon fibers as fillers are listed. It is done. Polyphenylene sulfide resins, polyether ether ketone resins, polyether imide resins, polybutylene terephthalate resins, polysulfone resins, polyether sulfone resins, polyacetal resins, and resins modified with glass fibers are suitable resins in the present invention. It is a material of the system. In particular, glass fiber reinforced polyphenylene sulfide resin not only has high Charpy impact strength and flexural modulus and low water absorption, but also has characteristics of long tensile creep life and low repeated vibration fatigue, and is a material for permeated water nozzles. Particularly preferred.
本発明において、透過水ノズルの金属配管は、ビクトリックジョイント接続、フランジ接続、クランプ接続等の接続方法により接続することができる。ネジ方式での接続も可能であるが、装着時、脱着時の作業性がよくなく、金属のネジ部との強い摩擦力で金属の場合に比べて損傷しやすいため、あまり好ましくない。 In the present invention, the metal pipe of the permeated water nozzle can be connected by a connection method such as a Victorian joint connection, a flange connection, or a clamp connection. Connection by a screw method is also possible, but it is not preferable because the workability at the time of attachment and detachment is not good, and it is easy to damage compared to the case of metal due to strong frictional force with the metal screw part.
本発明における逆浸透膜エレメントとは、圧力容器に装着し、供給水ノズル、濃縮水ノズル、透過水ノズルを設置することで、逆浸透膜モジュールとなるものである。圧力容器に装填される逆浸透膜エレメントの本数は逆浸透膜の種類により異なる。各逆浸透膜エレメントの透過水が個別の透過水ノズルから取り出される構造の場合は、逆浸透膜エレメントの劣化状況が反映された水質の透過水が透過水ノズルと接触されるため、逆浸透膜エレメントの劣化が進んだ場合は透過水ノズルへ腐食が顕著となり本発明の効果が現れやすい一例となる。この場合の逆浸透膜モジュール内に装填される逆浸透膜エレメントの本数は２本以内が実用上好ましい。 The reverse osmosis membrane element in the present invention is a reverse osmosis membrane module that is attached to a pressure vessel and provided with a supply water nozzle, a concentrated water nozzle, and a permeated water nozzle. The number of reverse osmosis membrane elements loaded in the pressure vessel varies depending on the type of reverse osmosis membrane. In the case where the permeated water of each reverse osmosis membrane element is taken out from an individual permeated water nozzle, the permeated water of water quality reflecting the deterioration state of the reverse osmosis membrane element is brought into contact with the permeated water nozzle. When the deterioration of the element progresses, the permeated water nozzle is significantly corroded, which is an example in which the effect of the present invention is likely to appear. In this case, the number of reverse osmosis membrane elements loaded in the reverse osmosis membrane module is preferably 2 or less.
本発明における酢酸セルロース系高分子としては、酢酸セルロース、三酢酸セルロース、両者の混合物が例としてあげられる。塩除去性能および透水性能、また、性能の安定性等から三酢酸セルロースが好ましい。酢酸セルロース系高分子は耐塩素性に優れるため、供給水に殺菌剤として塩素を添加することが可能である。塩素を含む原水を逆浸透膜に供給すると、透過水にも塩素が混入する。塩素の混入は透過水の腐食性を増す傾向にあるので、本発明の効果がよく発揮される事例である。 Examples of the cellulose acetate polymer in the present invention include cellulose acetate, cellulose triacetate, and a mixture of both. Cellulose triacetate is preferred from the standpoint of salt removal performance and water permeability, and stability of performance. Since the cellulose acetate polymer is excellent in chlorine resistance, chlorine can be added to the supply water as a bactericidal agent. When raw water containing chlorine is supplied to the reverse osmosis membrane, chlorine is also mixed into the permeated water. Since mixing of chlorine tends to increase the corrosivity of the permeated water, this is an example in which the effect of the present invention is well exhibited.
本発明における中空糸膜とは中空糸状の膜であり、その寸法は限定されない。海水淡水化用の中空糸型逆浸透膜モジュールの例としては、例えば、外径は１００μｍから３００μｍ、内径は中空糸膜の内径と外径とから算出される中空率も考慮して設定することが好ましく、例えば３０μｍから１５０μｍがあげられる。 The hollow fiber membrane in the present invention is a hollow fiber membrane, and its dimensions are not limited. As an example of a hollow fiber type reverse osmosis membrane module for seawater desalination, for example, the outer diameter is set to 100 μm to 300 μm, and the inner diameter is set in consideration of the hollow ratio calculated from the inner diameter and the outer diameter of the hollow fiber membrane. For example, 30 to 150 μm.
以下に、実施例を挙げて本発明を説明するが、本発明はこれらの実施例により何ら制限されるものではない。なお、実施例は、海水淡水化用の逆浸透膜の場合を示す。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In addition, an Example shows the case of the reverse osmosis membrane for seawater desalination.
（実施例１）
ポリフェニレンサルファイド樹脂にガラス繊維３０％を充填した複合材料からなる透過水ノズルを作製した。この複合材料の、シャルピー衝撃強さは１２ｋJ／m2、曲げ弾性率は８．８ＧＰa、吸水率は０．０１％であった。
この透過水ノズルについて、以下の脱着耐久性試験を実施した。すなわち、金属配管とビクトリックジョイントで装着・脱着を１００回実施し、その後、透過水ノズル内に水を充填し内圧１ＭＰａをかけ水漏れ発生の有無を観察した。脱着耐久試験後も水漏れは発生せず、また、透過水ノズルには変形および亀裂は発生していなかった。
さらに、金属配管とビクトリックジョイントで接合した状態で食塩１０００ｍｇ／Ｌの食塩水に６ケ月間接触させる腐食試験を実施した。透過水ノズルには腐食は観察されなかった。
結果を表１にまとめて示す。
Example 1
A permeated water nozzle made of a composite material in which 30% glass fiber was filled in polyphenylene sulfide resin was produced. This composite material had a Charpy impact strength of 12 kJ / m 2 , a flexural modulus of 8.8 GPa, and a water absorption of 0.01%.
The following desorption durability test was conducted on this permeated water nozzle. That is, mounting / desorption was performed 100 times with metal piping and a Victorian joint, and then water was filled in the permeated water nozzle and an internal pressure of 1 MPa was applied to observe the presence or absence of water leakage. Even after the desorption durability test, water leakage did not occur, and the permeated water nozzle did not deform or crack.
Further, a corrosion test was conducted in which the metal pipe was brought into contact with a 1000 mg / L saline solution for 6 months in a state where the pipe was joined with a Victoria joint. No corrosion was observed on the permeate nozzle.
The results are summarized in Table 1.
（実施例２〜６および比較例１〜７）
種々の樹脂系の材料により透過水ノズルを作製し、実施例１と同様の試験を実施した。結果を表１にまとめて示した。いずれの場合も腐食は観察されなかったが、曲げ弾性率の低いものは変形を生じて水漏れが発生した。また、シャルピー衝撃強さの低いものはビクトリックジョイント用の溝部分に亀裂が発生した。
(Examples 2-6 and Comparative Examples 1-7)
Permeated water nozzles were produced from various resin-based materials, and the same test as in Example 1 was performed. The results are summarized in Table 1. In either case, no corrosion was observed, but those with low flexural modulus were deformed and water leaked. In the case of low Charpy impact strength, cracks occurred in the groove part for the electric joint.
（実施例７）
三酢酸セルロース膜からなる中空糸型逆浸透膜を乾湿式紡糸法により作製し、外径１２０μｍ、内径４７μｍの中空糸膜を得た。この中空糸膜の脱塩性能を、３．５重量％の食塩水、中空糸膜有効長さ1m、供給水圧力５．４MPa、供給水温度２５℃、回収率２％で測定したところ、透過水量５６Ｌ／ｍ２／日、食塩除去率９９．８％であった。多孔管からなる供給流体分配管をその軸を中心に回転させ、これに中空糸膜の束をトラバースさせながら巻きつけることにより、中空糸膜を交差状に配置させ、中空糸膜の集合体を形成させた。この中空糸膜の集合体の両端部をエポキシ樹脂で封止固定した後、両端を切断して中空糸膜を開口させた。その後、供給流体分配管の内部に内部管を通し、両端部に設置される透過流体収集部材で固定して、中空糸膜エレメントを得た。この中空糸膜エレメントの中空糸膜集合体の外径は２６０ｍｍ、開口部間の軸方向の長さは１９９５ｍｍであった。左記中空糸膜エレメント２本を圧力容器に装填し、図１に示す膜モジュールを得た。図１では透過水ノズル１１および１１’のＯリング溝およびビクトリックジョイント接続用溝は省略して記載した。また、透過水ノズル１１および１１’には実施例１と同様の方法で製作したものを装着した。この膜モジュールを用い、実海水を供給水として１年間にわたり海水淡水化テストを実施した。左記運転期間中、透過水ノズル近傍からの水漏れは発生しなかった。また左記運転期間終了後、透過水ノズルを取り外して点検したところ、透過水ノズルに変形および亀裂は認められず、この透過水ノズルが高度な耐久性を持つことが実証された。
(Example 7)
A hollow fiber type reverse osmosis membrane composed of a cellulose triacetate membrane was prepared by a dry and wet spinning method to obtain a hollow fiber membrane having an outer diameter of 120 μm and an inner diameter of 47 μm. When the desalting performance of this hollow fiber membrane was measured at 3.5% by weight saline solution, the effective length of the hollow fiber membrane was 1 m, the feed water pressure was 5.4 MPa, the feed water temperature was 25 ° C., and the recovery rate was 2%. The amount of water was 56 L / m 2 / day, and the salt removal rate was 99.8%. By rotating a supply fluid distribution pipe comprising a perforated tube around its axis and winding the bundle of hollow fiber membranes while traversing them, the hollow fiber membranes are arranged in a crossing manner, and the assembly of hollow fiber membranes is formed. Formed. After sealing and fixing both ends of the hollow fiber membrane assembly with an epoxy resin, both ends were cut to open the hollow fiber membrane. Thereafter, the inner pipe was passed through the supply fluid distribution pipe and fixed with a permeating fluid collecting member installed at both ends to obtain a hollow fiber membrane element. The hollow fiber membrane assembly of this hollow fiber membrane element had an outer diameter of 260 mm, and the axial length between the openings was 1995 mm. Two hollow fiber membrane elements shown on the left were loaded into a pressure vessel to obtain a membrane module shown in FIG. In FIG. 1, the O-ring grooves of the permeated
本発明の逆浸透膜モジュールは、透過水の腐食性が高い場合でも腐食による損傷が発生せず、なおかつ振動や接触にも耐える機械的強度を有するため、海水淡水化や酸性水溶液の逆浸透処理等への利用が可能である。 The reverse osmosis membrane module of the present invention has a mechanical strength that does not cause damage due to corrosion even when the corrosiveness of the permeated water is high, and is resistant to vibration and contact. Etc. are possible.
１、１’：中空糸膜エレメント
２、２’：中空糸膜
３、３’：供給流体分配管
４ａ、４ｂ、４ａ’、４ｂ’：樹脂
５ａ、５ｂ、５ａ’、５ｂ’：中空糸膜開口部
６ａ、６ｂ、６ａ’、６ｂ’：透過流体収集部
７、７’：内部管
８：圧力容器
９：供給水ノズル
１０：濃縮水ノズル
１１、１１’：透過水ノズル
１２：供給水
１３：濃縮水
１４、１４’：透過水
１５：Ｏ−リング
１６：中間コネクタ
DESCRIPTION OF SYMBOLS 1, 1 ': Hollow
Claims (5)
The reverse osmosis membrane module according to claim 4 , wherein the reverse osmosis membrane comprises a hollow fiber type reverse osmosis membrane made of a cellulose acetate polymer.
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